CN100500279C - Denitrifying phosphorus-removing carrier and use - Google Patents
Denitrifying phosphorus-removing carrier and use Download PDFInfo
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- CN100500279C CN100500279C CNB2007100527946A CN200710052794A CN100500279C CN 100500279 C CN100500279 C CN 100500279C CN B2007100527946 A CNB2007100527946 A CN B2007100527946A CN 200710052794 A CN200710052794 A CN 200710052794A CN 100500279 C CN100500279 C CN 100500279C
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Abstract
The present invention belongs to the water treatment technical field and particularly relates to the preparation and use of a nitrogen and phosphorus removal carrier. The carrier of the present invention can provide the water environmental protection by the nitrogen and phosphorus removal treatment towards industrial wastewater and living sewage, which contain ammoniacal nitrogen and inorganic phosphorus, and towards pollution source or water in non-point source pollution. The nitrogen and phosphorus removal carrier of the present invention is characterized in that when a dry basis of the finished product is 200kg, and calculating according to weights, the components are as followings: 100kg to 120kg clinoptilolite powder, 90 percent of the exchange capacity over 100 meshes of which is more than 100cmol (plus)/kg; 50kg to 70kg land plaster, 90 percent of which is more than 100 meshes; 10kg industrial salt, the granular size of which is 2cm to 3 cm; 20kg common portland cement (labels of which is from 325 to 525); 2kg sawdust of pine tree; 100kg to 200kg complementary water. The present invention also discloses the preparation method and the application of the carrier.
Description
Technical field
The invention belongs to water-treatment technology field, particularly, the present invention relates to a kind of preparation and purposes of denitrifying phosphorus-removing carrier.Carrier of the present invention can carry out the water environment protection that denitrogenation dephosphorizing is handled to pollution sources (water) in the industrial wastewater, sanitary sewage and the pollution of area source that contain ammoniacal nitrogen, Phos etc.
Technical background
The generation of rivers, lake and reservoir water body eutrophication process mainly is the nitrogen and phosphorous nutrient (being mainly ammoniacal nitrogen and Phos) that contains in the sewage of importing above these water body self-purification abilities.The very important task in water environment protection field is taked effective technology exactly, is removed to a certain degree before nitrogenous phosphorus water source enters above-mentioned water body, to guarantee the ecological environment security of water body.
By retrieval, the application for a patent for invention of all kinds of sewage denitrification and dephosphorizations has the trend of accelerated growth in recent years in the Chinese invention patent, and present by retrieval relevant patent documentation is as follows:
Application number is preparation method and the application thereof that 200410084313 document discloses a kind of flyash synthetic zeolite, its core technology is that employing flyash is primary raw material, add and contain aluminium, siliceous, chloride or fluorine-containing etc. can be in alkaline solution dissolved substances, mixing the back adds metal base solution and by the synthetic coal ash zeolite of hydrothermal synthesis reaction, through activation transition of water miscible metal salt solution, makes the flyash synthetic zeolite after Separation of Solid and Liquid again; Utilize the flyash synthetic zeolite to ammonia nitrogen and phosphatic synchronous adsorption cleaning ability, realize the synchronous denitrification dephosphorizing of sewage is handled, also Powdered flyash synthetic zeolite directly can be added and in sewage, carry out synchronous denitrification dephosphorizing.This method needs complicated chemical reaction with raw material activation transition, makes the flyash synthetic zeolite after Separation of Solid and Liquid.
Application number is that 200510046987 documents disclose a kind of aerating biological filter pool filler and preparation method thereof, and it is primary raw material that this method adopts clay and diatomite, adds scum and carbon black on this basis; The percentage by weight of each component is as follows: sticking scholar 46.5%-87.5%, scum 11.5%-52.5%, carbon black 1.0-2.0%, diatomite 0-5.0%.Preparation method: with scum airing, ball milling, mistake 200 mesh sieves, mixed material; Filler granulation, particle diameter are 2-8mm, airing 2h; Filler is at 1100-1200 ℃ of roasting 20-30min; Filler sieves, puts in storage, this technology has improved the effect of biological aerated filter process denitrogenation dephosphorizing, nitrogen removal rate than ceramic grain filter improves 20%, total tp removal rate has improved 5%, and realized refuse reclamation, reduce the cost of raw material at least 10%, but this method needs to raw material ball milling and high-temperature calcination.
Application number is the preparation method that 200510048671 document discloses a kind of adsorption agent for sewage denitrification and dephosphorization, its technical process is for being 60-100 purpose powdery zeolite with granularity, diatomite or aluminium oxide, in distilled water, soak 15-30min, filtering the back dried 1-2 hour under 100-430 ℃ of temperature, solid-liquid weight ratio according to design adds in the rare-earth hydroxide solution for preparing, normal temperature stirred 45-60 minute down, left standstill dipping 15-20 hour, solution is filtered, obtain filter cake and filtrate, filter cake is through temperature 300-600 ℃, and time 0.5-2h roasting obtains the adsorbent of aperture 0.3nm-0.5nm after screening.This adsorbent can remove nitrogen and the phosphorus in the decontaminated water simultaneously, adsorption capacity to nitrogen reaches 15-20mg/g, adsorption capacity to phosphorus reaches 22-25mg/g, adsorb adsorbent after saturated behind alkali liquid regeneration, adsorption capacity only reduces 6%-7%, this method not only will be carried out chemical reaction earlier with raw material, and material also need pass through filtration, roasting after pulverize, just can make after the screening then, and still needs roasting during regeneration.
Application number is the renovation process that 200610010634 documents disclose a kind of rare-earth adsorbent after sewage denitrifying and dephosphor, this method is the saturated rare-earth adsorbent that will be applied to behind the sewage denitrification and dephosphorization, elder generation's spent regeneration solution is that the weight ratio of the sodium chloride solution of concentration 0.5-3mol/L, saturated rare earth adsorbent and actified solution is 1:50-70, is the desorption processing that circulates of the actified solution of 2-5m/h with the linear speed, regulate actified solution pH value between 8-14 with alkali lye in the processing procedure, desorption 3-4 hour; Filter, use activating solution that the rare earth element identical with this saturated rare-earth adsorbent be mixed with to desorption again after rare-earth adsorbent carry out the cyclic activation impregnation process; Refilter, obtain regeneration then behind the drying and roasting, its adsorption capacity reaches more than 90% of former adsorbent.Its defective not only will be carried out chemical reaction earlier with raw material as above-mentioned method, material also need pass through filtration, roasting after pulverize, just can make after the screening then, and still needs roasting during regeneration.
Application number is that 200610010644 documents disclose a kind of modified natural and self-control floating carrier and mesopore molecular sieve denitrogen dephosphorization material, preparation and application, this denitrogenation dephosphorizing material comprises that lanthanum ion, cerium ion, metallic aluminium ion, calcium ion or its are combined as 5-33%, and surplus is the Large ratio surface lightweight aggregate; Lanthanum ion, cerium ion, metallic aluminium ion, calcium ion or its are combined as 3-20%, the combination 50-85% of Large ratio surface lightweight aggregate, flyash 5-10%, surfactant 0.5-1%, cement 1-5%, and surplus is a double-ash powder; Lanthanum ion, cerium ion, metallic aluminium ion, calcium ion or its are combined as 10-50%, and surplus is a silicon-based mesoporous molecular sieve.Preparation gained adsorbent specific surface is big, adsorption capacity is high, the efficient height.Though this method also is a preparation denitrogenation dephosphorizing material, the preparation raw material is a rare earth element, and this preparation method has improved the adsorbent production cost virtually.
Application number is 200610086102 to disclose the method that a kind of immobilized sludge is removed nitrogen, phosphorus in the eutrophication water, this invention is fixed on the acclimation sludge embedding by immobilization technology and makes the immobilized sludge bead on the carrier, and to its pre-Anaerobic Treatment, the denitrogenation dephosphorizing that pretreated immobilized sludge bead is used for eutrophication water is handled.Wherein the carrier of immobilized sludge is a sodium alginate, and the mud of embedding is the high-efficient denitrification and dephosphorization mud of taming voluntarily.This method has good denitrogenation dephosphorizing effect when handling eutrophication water, Separation of Solid and Liquid is easy, although this method is that adsorbent is prepared into the particle bead, but adsorbent itself is a kind of mud, its absorption property can change along with the variation of sludge characteristics, so its removal effect to nitrogen phosphorus is difficult to stable.
The denitrogenation dephosphorizing material of above-mentioned removal sewerage nitrogen and phosphor (or claim adsorbent or claim carrier) is though all have higher removal to nitrogen phosphorus, preparation process complexity separately.In addition, all do not show the concentration range of each self application denitrogenation dephosphorizing in the existing patent, patent open insufficient makes those skilled in the art be difficult to implement its invention and reach the alleged invention effect of invention according to specification.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, it is good to develop a kind of absorption property, and preparation technology is simple, a kind of carrier of removing sewerage nitrogen and phosphor that preparation cost is lower.The denitrifying phosphorus-removing carrier mechanical strength height of the present invention preparation can be removed nitrogen and phosphorus in the sewage simultaneously, the clearance height, and non-secondary pollution satisfies the needs of current waste water control.
The present invention is achieved in that
Carrier of the present invention is a major ingredient with natural zeolite, gypsum, is aided with raw materials such as cement, low-diet salt, pine sawdust, and by the material mixing, add water plasticizing, denitrifying phosphorus-removing carrier (its preparation technology and technology path are referring to Fig. 1) is processed in moulding pore-creating.The natural zeolite powder of implementing core technology of the present invention and be to have higher cation exchange capacity (CEC) adds a certain proportion of land plaster with the abundant mixing of agitator, add earlier in whipping process that low-diet salt adds a certain proportion of cement behind the mixing gradually again and the pine sawdust stirs evenly, when mixed material is not seen heterogeneity, it is mixed that gradual slow adds a certain amount of clear water, treat to stop when plasticity appears in material mixing, material is squeezed into ball type carrier with the coal briquette nodulizer.Ball type carrier after the moulding adds water logging and did not soak for 1 week, and therebetween, stir half an hour with filler particles every day, then discards immersion water, is denitrifying phosphorus-removing carrier of the present invention after carrier drains.
Concrete technical scheme of the present invention is:
A kind of denitrifying phosphorus-removing carrier, component by weight is as follows:
In the manufactured goods butt is 200kg:
Clinoptilolite powder (90% crosses 100 order exchange capacities at 100cmol (+)/more than the kg) 100～120kg
Land plaster (90% crosses 100 orders) 50～70kg
Industrial salt (particle diameter 2-3cm) 10kg
Portland cement (label 325-525) 20kg
Pine tree sawdust 2kg
Replenish clear water 100-200kg
Prepare according to the following step:
1) by prescription clinoptilolite powder and land plaster are mixed 5～10min with the powder mixer, obtain material 1;
2) under stirring condition, in material 1, add industrial salt, Portland cement, the pine tree sawdust continues to mix, and has not with the material that is invisible to the naked eye that the mixing sign is as the criterion, and obtains material 2;
3) with step 2) material 2 of gained under agitation sprays clear water, observes material and plasticity occurs and be as the criterion, and obtains material 3;
4) the material 3 usefulness Squeezinggranulators of step 3) gained are made the spherical fresh carrier of 3～5cm;
5) the fresh carrier water with the step 4) gained floods, and makes carrier pore-creating, and the interior cement of carrier is hardened gradually;
6) carrier and the water with the submergence of step 5) institute stirs 30min together every day, makes the carrier compression strength of preparation reach 65～75N, and it is standby to drain this carrier.
According to aforesaid preparation method, the prescription of one of them optimization, component by weight is as follows:
In the manufactured goods butt is 200kg:
Clinoptilolite powder (90% crosses 100 order exchange capacities at 100cmol (+)/more than the kg) 100kg
Land plaster (90% crosses 100 orders) 70kg
Industrial salt (particle diameter 2-3cm) 10kg
Portland cement (label 425) 20kg
Pine tree sawdust 2kg
Replenish clear water 200kg.
According to aforesaid preparation method, the prescription of another optimization wherein, component by weight is as follows:
Clinoptilolite powder (90% crosses 100 order exchange capacities at 100cmol (+)/more than the kg) 110kg
Land plaster (90% crosses 100 orders) 60kg
Industrial salt (particle diameter 2-3cm) 10kg
Portland cement (label 325) 20kg
Pine tree sawdust 2kg
Replenish clear water 150kg.
According to aforesaid preparation method, Zui Jia prescription wherein, component by weight is as follows:
In the manufactured goods butt is 200kg:
Clinoptilolite powder (90% crosses 100 order exchange capacities at 100cmol (+)/more than the kg) 120kg
Land plaster (90% crosses 100 orders) 50kg
Industrial salt particle diameter (2-3cm) 10kg
Portland cement (label 525) 20kg
Pine tree sawdust 2kg
Replenish clear water 100kg.
The denitrifying phosphorus-removing carrier of the present invention's preparation has good economic benefit, according to the market constant price, 1 ton of this denitrifying phosphorus-removing carrier of every production (containing 50% zeolite, 35% gypsum, 5% industrial table salt and 10% cement) needs the material cost expense to be roughly equal to 257 yuan of RMB approximately.
The denitrifying phosphorus-removing carrier of the present invention's preparation has good result of use, calculates according to mass balance, and under the prerequisite of the exchangeability quality that guarantees zeolite, but the NH of carrier intercept process 4～5kg per ton
4 +-N, the NH that is blocked
4 +-N generates N by denitrification in carrier
2And be removed.Therefore, theoretically, carrier can make repeatedly in denitrogenation; Carrier per ton can be removed the 55.8kg Phos, to sewage (the flow 0.05m of phosphorous 0.25mg/L
3/ s) interception result of middle phosphorus can be for 10 years.
The kinetics experiment shows that denitrifying phosphorus-removing carrier of the present invention is to NH
4 +The speed constant of-N interception is 0.02h
-1, interception 4mg/L NH
4 +The half-life of-N, the speed constant of removing Phos was 0.2～0.3h between 34～37h
-1Between, the half-life of removing the 5mg/L Phos is between 3～4h.
Know-why of the present invention is:
Some natural minerals such as zeolite have the ability of catching inorganic ions.Zeolite has good heat endurance, acid resistance, heat-resisting quantity, radiation hardness characteristic, prior ion exchange property in addition, and this specific character can make NH in the zeolite exchange solution
4 +Except the mineral of exchangeability, some mineral has microsolubility.Gypsum is a kind of microsolubility mineral, and its solubility is than high 4 orders of magnitude of calcium carbonate, and is than high 3 orders of magnitude of phosphoric acid one fine particle calcium carbonate, higher than calcium phosphate.Therefore, gypsum and dissolubility Phos are put together, just can make gypsum be converted into calcium phosphate, thereby remove the Phos in anhydrating.The present invention uses zeolite, gypsum dexterously, and these have the mineral of special nature, are prepared into denitrifying phosphorus-removing carrier of the present invention.
The invention has the beneficial effects as follows:
1) denitrifying phosphorus-removing carrier preparation process of the present invention is very simple, and feed product mixing, mixed moulding, sclerosis are got final product, and energy consumption is low and cost of material is low;
2) the present invention has taken into full account carrier interception NH
4 +(carrier is introduced the pine sawdust to the bio-degradable of-N, is NH
4 +The biodegradation of-N provides carbon source);
3) the present invention's usefulness cement has guaranteed the mechanical strength of carrier as the adhesive of carrier, as pore creating material, has guaranteed the porous of carrier with industrial table salt conscientiously, has improved the contact-making surface of carrier and sewage.
Description of drawings
Fig. 1: be technology of the present invention and technology path flow chart.
Fig. 2: the denitrogenation kinetic curve of implementation result that is the carrier of the embodiment of the invention 1, embodiment 2, embodiment 3 preparations.
Fig. 3: the dephosphorization kinetic curve of implementation result that is the carrier of the embodiment of the invention 1, embodiment 2, embodiment 3 preparations.
The specific embodiment
Embodiment 1
A kind of denitrifying phosphorus-removing carrier, component by weight is as follows:
In the manufactured goods butt is 200kg:
Clinoptilolite powder (90% crosses 100 order exchange capacities at 100cmol (+)/more than the kg) 100kg
Land plaster (90% crosses 100 orders) 70kg
Industrial salt (particle diameter 2-3cm) 10kg
Portland cement (label 425) 20kg
Pine tree sawdust 2kg
Replenish clear water 200kg.
Prepare according to the following step:
1) by prescription clinoptilolite powder and land plaster are mixed 5～10min with the powder mixer, obtain material 1:
2) under stirring condition, in material 1, add industrial salt, Portland cement, the pine tree sawdust continues to mix, and has not with the material that is invisible to the naked eye that the mixing sign is as the criterion, and obtains material 2;
3) with step 2) material 2 of gained under agitation sprays clear water, observes material and plasticity occurs and be as the criterion, and obtains material 3;
4) the material 3 usefulness Squeezinggranulators of step 3) gained are made the spherical fresh carrier of 3～5cm;
5) the fresh carrier water with the step 4) gained floods, and makes carrier pore-creating, and the interior cement of carrier is hardened gradually;
6) carrier and the water with the submergence of step 5) institute stirs 30min together every day, makes the carrier compression strength of preparation reach 65～75N, and it is standby to drain this carrier.
The prepared denitrifying phosphorus-removing carrier of present embodiment is 0.0188h in the first order reaction speed constant of denitrification process
-1, the half-life is 37h; The first order reaction speed constant of dephosphorization process is 0.1923h
-1, the half-life is 4h.
Embodiment 2
According to the preparation method of embodiment, present embodiment is the prescription of wherein another optimization, and component by weight is as follows;
Clinoptilolite powder (90% crosses 100 order exchange capacities at 100cmol (+)/more than the kg) 110kg
Land plaster (90% crosses 100 orders) 60kg
Industrial salt (particle diameter 2-3cm) 10kg
Portland cement (label 325) 20kg
Pine tree sawdust 2kg
Replenish clear water 150kg.
The prepared denitrifying phosphorus-removing carrier of present embodiment is 0.0197h in the first order reaction speed constant of denitrification process
-1, the half-life is 35h; The first order reaction speed constant of dephosphorization process is 0.3395h
-1, the half-life is 2h.
Embodiment 3
Present embodiment is a preferred forms of the present invention, and according to the preparation method of embodiment, its prescription component by weight is as follows:
In the manufactured goods butt is 200kg:
Clinoptilolite powder (90% crosses 100 order exchange capacities at 100cmol (+)/more than the kg) 120kg
Land plaster (90% crosses 100 orders) 50kg
Industrial salt particle diameter (2-3cm) 10kg
Portland cement (label 525) 20kg
Pine tree sawdust 2kg
Replenish clear water 100kg.
The prepared denitrifying phosphorus-removing carrier of present embodiment is 0.0205h in the first order reaction speed constant of denitrification process
-1, the half-life is 34h; The first order reaction speed constant of dephosphorization process is 0.2191h
-1, the half-life is 3h.
According to technical scheme provided by the invention and embodiment, denitrifying phosphorus-removing carrier of the present invention generally is prepared to ball type carrier, this carrier ball can be positioned over during use in the channel that sewage passes through, form so-called " biological gallery ", reach the purpose of sewage denitrification and dephosphorization.Also can described carrier ball adorned, place the hydrostatic pond, reach the purpose of denitrogenation dephosphorizing equally with netted container.
Claims (5)
1, a kind of carrier that removes ammoniacal nitrogen and Phos is characterized in that, component by weight is as follows:
In the manufactured goods butt is 200kg:
The clinoptilolite powder, 90% crosses 100 orders, and exchange capacity is at 100cmol (+)/100～120kg more than the kg
Land plaster, 90% crosses 100 orders, 50～70kg
Particle diameter is the industrial salt 10kg of 2-3cm
Portland cement, label 325-525 20kg
Pine tree sawdust 2kg
Replenish clear water 100-200kg
Prepare according to the following step:
1) by prescription clinoptilolite powder and land plaster are mixed 5～10min with the powder mixer, obtain material 1;
2) under stirring condition, in material 1, add industrial salt, Portland cement, the pine tree sawdust continues to mix, and has not with the material that is invisible to the naked eye that the mixing sign is as the criterion, and obtains material 2;
3) with step 2) material 2 of gained under agitation sprays clear water, observes material and plasticity occurs and be as the criterion, and obtains material 3;
4) the material 3 usefulness Squeezinggranulators of step 3) gained are made the spherical fresh carrier of 3～5cm;
5) the fresh carrier water with the step 4) gained floods, and makes carrier pore-creating, and the interior cement of carrier is hardened gradually;
6) carrier and the water with the submergence of step 5) institute stirs 30min together every day, makes the carrier compression strength of preparation reach 65～75N, and it is standby to drain this carrier.
2, a kind of carrier that removes ammoniacal nitrogen and Phos according to claim 1,, it is characterized in that component by weight is as follows:
In the manufactured goods butt is 200kg:
The clinoptilolite powder, 90% crosses 100 orders, and exchange capacity is at the above 100kg of 100cmol (+)/kg
Land plaster, 90% crosses 100 order 70kg
Particle diameter is the industrial salt 10kg of 2-3cm
Portland cement, label 425 20kg
Pine tree sawdust 2kg
Replenish clear water 200kg.
3, a kind of carrier that removes ammoniacal nitrogen and Phos according to claim 1,, it is characterized in that component by weight is as follows:
In the manufactured goods butt is 200kg:
The clinoptilolite powder, 90% crosses 100 orders, and exchange capacity is at the above 110kg of 100cmol (+)/kg
Land plaster, 90% crosses 100 order 60kg
Particle diameter is the industrial salt 10kg of 2-3cm
Portland cement, label 325 20kg
Pine tree sawdust 2kg
Replenish clear water 150kg.
4, a kind of carrier that removes ammoniacal nitrogen and Phos according to claim 1 is characterized in that component by weight is as follows:
In the manufactured goods butt is 200kg:
The clinoptilolite powder, 90% crosses 100 orders, and exchange capacity is at the above 120kg of 100cmol (+)/kg
Land plaster, 90% crosses 100 order 50kg
Particle diameter is the industrial salt 10kg of 2-3cm
Portland cement, label 525 20kg
Pine tree sawdust 2kg
Replenish clear water 100kg.
5, each described carrier of claim 1-4 removes the purposes of ammoniacal nitrogen and Phos in nitrogenous and phosphorous water environment.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100527946A CN100500279C (en) | 2007-07-20 | 2007-07-20 | Denitrifying phosphorus-removing carrier and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100527946A CN100500279C (en) | 2007-07-20 | 2007-07-20 | Denitrifying phosphorus-removing carrier and use |
Publications (2)
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| CN100500279C true CN100500279C (en) | 2009-06-17 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935195B (en) * | 2010-09-01 | 2012-07-25 | 郑俊 | Porous phosphorus removing ceramic granules with function of slowly releasing alkali and preparation method thereof |
| CN102173506B (en) * | 2011-03-21 | 2013-01-23 | 尹军 | Bioactive compound filling material |
| CN102151548B (en) * | 2011-04-22 | 2012-07-25 | 湖北富邦科技股份有限公司 | Adsorption material for treating phosphorus wastewater and use thereof |
| CN103331145B (en) * | 2013-07-08 | 2014-12-31 | 湖北富邦科技股份有限公司 | Preparation method of heavy metal ion absorbent from phosphogypsum |
| CN103721667B (en) * | 2013-12-17 | 2015-08-26 | 江苏省农业科学院 | A kind of dephosphorization adsorbent and preparation method efficiently |
| CN104860360A (en) * | 2015-05-19 | 2015-08-26 | 东北师范大学 | Device for blocking farmland non-point source pollution in river basin |
| CN108236912A (en) * | 2016-12-27 | 2018-07-03 | 中国科学院宁波城市环境观测研究站 | It is a kind of except adsorbent of water systems'phosphorus and preparation method thereof |
| CN116371372B (en) * | 2023-05-25 | 2024-05-28 | 中国长江三峡集团有限公司 | Method for preparing adsorption material by utilizing sodium alginate reinforced ditch sludge screening product and prepared adsorption material |
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